Process for imparting to a cellulosic textile resistance to rot and weathering



United States Patent 3,420,699 PROCESS FOR IMPARTING TO A CELLU- LOSIC TEXTILE RESISTANCE TO ROT AND WEATHERING Hubert H. St. Mard, New Orleans, and Carl Hamalainen and Albert S. Cooper, Jr., Metairie, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Apr. 22, 1966, Ser. No. 544,370 US. Cl. 117-1385 9 Claims Int. Cl. D06m 13/50; D06m 13/34 A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to a process for imparting rot and weather resistance to cellulosic textiles. More specifically this invention relates to a process for imparting rot and weather resistance to cellulosic textiles by treating the said cellulosic textiles with aminoplast resins, wherein the reaction is catalyzed with metallic salts such as zirconyl acetate, zirconyl ammonium carbonate, zirconyl sulphate, and the like. For purposes of the present invention an aminoplast resin is one which is a condensation product of an amine and an aldehyde.

It is understood to include all arninoplasts formed as reaction products of 1 mole of melamine with from 1 to 6 moles of formaldehyde; and also the methylated derivatives of these reaction products.

The cellulosic textiles treated by process of this invention find use in the fabrication of awnings, boat covers, canvas tops, tarps, shade umbrellas, shoe liners, irrigation liners, agricultural shade cloth and covers, and the like. All areas of use which may be inhibited by outdoor or indoor bacterial, fungal, and/or actinic degradation will find beneficial application due to this process.

One object of this invention is to provide a process for imparting rot resistance to cotton and other cellulosic textiles.

It is within the scope of this patent to include all cotton cellulosic fabrics such as printcloth, army duck, sateen, canvas, tenting, tarpaulins, belts, etc., either in a greige or scoured stage.

Also included are scoured or greige cotton yarns of all sizes. It is also understood to include all other cellulosics such as linen, hemp, ramie, jute, rayon, regenerated fibers, and chemically modified and/or blended fibers or fabrics.

Another object of this invention is to provide a process for imparting actinic degradation resistance to cotton and other cellulosic textiles.

A third object of this invention is to provide a process for imparting to cotton and other cellulosic textiles both the said rot resistance and the said actinic degradation resistance by treating the said cotton or other cellulosic textiles with an aminoplast resin wherein the reaction is catalyzed by a metallic salt such as zirconium acetate or the like.

A fourth object of this invention is to provide a process for imparting to cotton and other cellulosic textiles resistance to degradation by microbial attack, specifically the rotting caused by soil bacteria and the soiling caused by algae growth.

The prior art teaches that the formic acid colloid of methylolmelamine, as used by Berard et al., (was used to treat cellulose in the form of cotton fabric in order to thereby render it resistant to actinic attack. Because of the treatment the products by Berards process suffer considerably from loss of strength. The usual losses being about 2030%. This loss is incurred by the fabric during the treatment.

We have now discovered that in imparting the rot and weather resistance to cotton and other cellulosic textiles we have not only achieved this goal but also minimized the losses which are generally imparted by a similar treatment. Furthermore, we find, unexpectedly, that in some instances by the process of our present invention we have treated some textiles with no strength losses whatever due to the treatment. Also, these treated textiles have exhibited a considerable degree of softness of hand therefore making the addition of softeners in our pad bath unnecessary.

Investigating the prior art further we found that Ruperti in 1956 disclosed in US. Patent 2,763,574 the use of a steaming or wet aging (of aminoplast resins) process to provide microbiological protection to cotton yarn. The process cannot be considered economically feasible in most instances because textile plants generally are not equipped for the steaming process nor the space required for the wet aging. Both B'erard and .Rupertis processes are unsatisfactory in that an algaecidal substance must be added to their formulation in order to inhibit the algae growth and its discoloration which renders the textile unattractive. Furthermore the additive must not react with the reagents.

Our formulation requires no additives, since the catalyst serves in two capacities, that is, it catalyzes the polymerization reaction and is incorporated into the final product, thereby imparting to the fabric algaestatic and algaecidal properties to supplement the other weathering characteristics acquired in the treatment. We have found that not only is algae growth minimized but consistently in exposing samples to 12 months weathering We have found that no algae growth whatever has been exhibited by the exposed samples.

One of the chief causes of actinic degradation has been attributed by those skilled in the art to ultraviolet light. We have found that by process of our invention ultraviolet light is screened out by the polymer formed within treated cellulosic fibers. The catalyst, which is zirconyl acetate or the like, in addition to supplementing the screening of the ultraviolet rays which is the main function of the polymer, also acts as an algaecidal agent.

We have used titanium dioxide (rutile) in several of our applications as an additive sunlight screener.

Further in contrast to the processes and methods of application of the prior art the process of our invention offers a rapid and economical treatment with an efiicient method of application.

In general the preparation and application of our invention can be described as follows: An aqueous solution of an aminoplast, such as trimethylolmelamine, methylated methylolmelamine or other condensation products of amine and aldehyde, is prepared and a suitable catalyst, such as zirconyl acetate, is added to the solution. The aminoplast concentration can be about from 5 to 20%, but our preferred concentration is about 17%. The zirconyl acetate, which is our preferred catalyst for the process of this invention is available in acetic acid solution, containing 58.5% zirconyl acetate corresponding to 22% ZrO content. The catalyst concentration can be about 4 to 14%; but our preferred concentration is about 8% based on the total weight of the formulation.

To the above solution a wetting agent, such as Triton X-100 (an alkyl aryl ether alcohol), is incorporated in a quantity about 0.2% by weight of total mixture.

Although polymerization can be affected by acetic acid it does not yield the ac-ceptacle rot and weather resistant product as when zirconyl acetate is present.

The application of the chemicals to the textiles is generally a conventional padding, squeezing of excess solution, drying, and curing. The drying of the fabric previous to cure need not be complete. In fact reducing it to 5-15 moisture content is very satisfactory and this can be accomplished in about 3-5 minutes at about 75 C. to 95 C. Mills with high capacity ovens can reduce this time considerably. Curing can be done in about 4-8 minutes atabout 120 C. to 160 C. The preferred time and temperature of drying are 4 minutes at 80 C., while the preferred curing time and temperature are 4 minutes at 140 C.

The final product is generally analyzed for nitrogen content, and this figure is correlated with the weight add-on. We have learned in the process of investigation that our process works most suitably when the nitrogen content is about from 3% to 6%, and the optimum is 5%.

In a stability study in order to determine the optimum concentration of zirconyl acetate needed to cause polymerization of trimethylolmelamine some very unexpected results were obtained. The concentration of trimethylolmelamine was kept constant (16.7%) and only the amount of zirconyl acetate was varied. It was found that when a small amount of zirconyl acetate was used (less than 4%) a rapid polymerization of the resin took place. This also happened when large amounts of catalyst were used (above 14%). It was decided from this study to employ zirconyl acetate to the extent of 8% since it results in a stability of about 35 min. which is ample time for padding a considerable amount of textile fabric on the usual textile machinery.

In contrast to this comparatively short term stability zirconyl acetate solution was used as a catalyst modifier with Aerotex M-3, Resin 841 and Aerotex 23. These products are methylated methylolmelamines. The results of these applications showed resin add-on of from 10 to 16% and the solutions were stable from about 1% hrs. to over 4 hrs. Also the apparent shortcoming due to limited stability of the zirconium acetate catalyzed trimethylolmelamine can be circumvented by a change in application technique. This is accomplished by a separate padding procedure. An aqueous solution of trimethylolmelamine containing a wetting agent is used to pad the fabric. Immediately following this the wet fabric is now padded through an aqueous solution of zirconyl acetate. Since each of these paddings are separate and independent of each other there is no problem of resin bath stability.

Our preferred formulation consists of these quantities or equally proportional gravimetric quantities. For example when we use 412.8 grns. of trimethylolmelamine we mix 1670.2 gms. of water and 313.0 gms. of zirconyl acetate solution (of 58.5% zirconyl acetate content) which we employ as a catalyst and supplemental modifier. We refer to this as our 20% solids content formulation, accounting for the fact that on curing the zirconyl acetate decomposes to the oxide.

We have exposed samples treated with our preferred formulation to weathering together with appropriate controls, and unexpectedly have found that no strength losses were evident in the material which was treated with the 20% solids formulation of our invention after weathering for 12 months. The controls were found to be only of their original values. In further testing of our preferred formulation treatment we submitted the treated samples to a standard soil burial test. Samples treated with 11% solids concentration were found to have lost only 35% of their strength in 6 weeks exposure to the soil bed, while the samples which were treated with our 20% formulation were found to have retained 100% of their strength after exposure to soil burial for the same time. The untreated controls in this test rotted completely before one weeks exposure.

We have found that our treatment of cellulosic textiles imparts to the said cellulosic textiles satisfactory resistance to weather in total solids concentrations about from 11% to 25%. Although we generally dry the impregnated material prior to curing, we have found that the drying and curing can be combined into one continuous operation. The drying is usually carried out at about C. for about 4 min. and the cure is generally for 4 min. at about 140 C. The combined operation could be accomplished by dry-cure of the wet impregnated textiles for about 4-8 min. at about 100110 C. Our preferred method of applying our formulation to the cellulosic material consists of wetting the material with the aqueous mixture at room temperature pressing out excess solution then curing in a standard oven for 4 min. at 140 C. or an equivalent time and temperature. The washing and drying operation generally follows this treatment.

Another method of affecting the cure of cellulosic fabrics padded with aminoplast resins and using zirconyl acetate as catalyst and modifier is the delayed cure process.

In the delayed cure process the fabric after having excess liquid expressed by the squeeze rollers of the padder is given a low temperature drying, e.g. 6085 C. for from 36 min.

The fabric is then left at room temperature for from several days to 30 days during which time the polymerization effectively takes place. The fabric may now be washed or used without washing for all types of outdoor uses.

The present invention can best be described as three separate and distinct processes (A, B, and C), each with a similar and a dissimilar useful facet, each useful under different conditions.

Process A is a process for imparting to cellulosic textiles resistance to rot and weathering comprising the following steps:

(a) wetting the cellulosic textile with an aqueous solution containing about from 8 to 17.2% by weight of an aminoplast resin selected from the group consisting of trimethylolmelamine and methylated methylolmelamine, about 13% of zirconyl acetate catalyst (22% ZrO and about 0.2% of a wetting agent,

(b) removing excess solution to obtain a wet pickup of about from 70% to (c) drying the wet cellulosic textile at about from 75 to C. for about from 3 to 5 minutes of time, the lower temperatures used with the longer periods of time, and

(d) curing the dry cellulosic textile at about from to C. for about from 4 to 8 minutes of time, the lower temperatures used with the longer periods of time.

Process B is a process for imparting to cellulosic textiles resistance to rot, weathering, and actinic degradation comprising the following steps:

(a) wetting the cellulosic textile with an aqueous mixture containing about from 8 to 17.2% by weight of an aminoplast resin selected from the group consisting of trimethylolmelamine and methylated methylolmelamine, about 13% of zirconyl acetate catalyst (22% ZrO about 0.2% of a wetting agent, and about 3% of titanium dioxide,

(b) removing excess solution to obtain a wet pickup of about from 70% to 90%,

(c) drying the wet cellulosic textile at about from 75 to 95 C. for about from 3 to 5 minutes of time, using the lower temperatures with the longer periods of time, and

(d) curing the dry cellulosic textile at about from 120 to 160 C. for about from 4 to 8 minutes of time, using the lower temperatures with the longer periods of time.

Process C is a departure from Processes A and B only in that the ingredients are applied from two solutions rather than from one mixture. Process C is preferred whenever the amount of fabric to be treated exceeds the amount of fabric which can be treated within a time limit in which polymerization of the ingredients occurs. The steps of Process C comprise (a) wetting the cellulosic textile with an aqueous solution containing about 17.2% by weight of an aminoplast resin selected from the group consisting of trimethylolmelamine and methylated methylolmelamine, and about 0.2% of a wetting agent,

(b) removing excess solution to obtain a wet pickup of about from 60% to 80%,

(0) further wetting the wet cellulosic textile from (b) with an aqueous solution containing about 30% of zirconyl acetate catalyst,

(d) removing excess of mixture of solutions to obtain a wet pickup of about from to higher than the wet pickup obtained in step (b),

(e) drying the wet cellulosic textile at about from to C. for about from 3 to 5 minutes of time, using the lower temperature with the longer periods of time, and

(f) curing the dry cellulosic textile at about from to 160 C. for about from 4 to 8 minutes of time, using the lower temperatures with the longer periods of time.

The employment of the ingredients of Process A to illustrate the steps of Process C, above, does not preclude the employment of the ingredients of Process B or other similar formulations with like substances.

Process C is specifically illustrated in Example 11. A limited amount of cotton fabric was employed in carrying out the process. The fabric was padded with an aqueous solution containing only the aminoplast resin and the wetting agent. The fabric, still wet with the first solution, was then padded with the aqueous solution, which contained the zirconyl acetate. The fabric was then submitted to the ordinary drying, curing, and washing. Example 11 teaches that when the reactants are kept separated the reaction does not take place until immediately before contact with the fabric and the contact is made in successive steps only. This particular procedure is advantageous when the time of treating the fabric is greater than the time limit of the pad bath stability of resin-catalyst solution.

When the amount of cellulosic fabric to be treated is larger than that shown in Example 11 of this specification a practical procedure would be to pad the fabric through an aqueous resin solution to a wet pickup of about 60% to 80%, and then to pad the wet fabric with a zirconyl acetate solution, employing a conventional padder with minimum volume immersion capacity. A horizontal roll padder or a padder with an immersion tank requiring 3 to 10 gallons of solution for operation is satisfactory. The volume of the zirconyl acetate padding solution is maintained at a constant level either by overfeeding or by a float valve arrangement. The total wet pickup from the second padder is about from 10% to 30% effectively prevents any significant amount of polymer formation in the tank of the padder. The low volume of the padder tank permits the reagents to reach equilibrium rapidly without deterioration of the solution.

Another method somewhat similar to the above and used for the same purpose is that of metering the separate solutions to a tank that feeds the pad bath. The level of reaction mixture in the bath is kept constant, and the fabric is padded through at a speed sufiicient to exhaust the contents in such time that is significantly less than the time of stability of the mixture. Since the bath is fed at a speed to keep it at constant level, in effect, it is constantly replenished by new reactants which effectively prevent polymer formation in the padding solution.

EXAMPLE 1 To 1670.2 grams of distilled water at room temperature was added with continuous stirring 4128 grams of trimethylolmelamine powder. After complete dissolution was attained 5 grams of a wetting agent, Triton X-100 (an alkyl aryl ether alcohol) was added to ensure complete penetration of the cotton fabric to be treated. To this solution was added 312.0 grams of zirconyl acetate as an acetic acid solution of 58.5% zirconyl acetate. This solution was added immediately prior to the treatment of the textile due to the time limit of stability of the pad bath. This amount of zirconyl acetate corresponds to 68.6 grams of ZrO on a solids basis, and the entire formulation consists of 20% solids.

An 80 x 80 cotton printcloth was padded with the above solution with sufficient roll pressure on the squeeze rolls to obtain a wet pickup of 80%. Following the padding operation the fabric was given a preliminary drying for 4 minutes at 80 C. in a gas fired oven, then an immediate cure for 4 minutes at C. in the same oven. The treated sample was then washed to remove any unreacted or loosely bound chemicals, then dried.

The finished fabric had a final weight add-on of 14.6%, and a nitrogen content of 5.3%, determined by the Kjeldahl method. Physical property comparisons are shown in Tables I and II.

EXAMPLE 2 To 1795 grams of distilled water at room temperature was added with continuous stirring 288 grams of trimethylolmelamine powder. To this solution was added 5.0 grams of Triton X-100 and 312 grams of zirconyl acetate solution. This formulation has 14.9% solids content and was used to treat the same kind of material as in Example 1, and in similar manner. Physical property comparisons are shown in Tables I and II.

EXAMPLE 3 To 1875 grams of distilled water at room temperature Was added with continued stirring 192 grams of trimethylolmelamine powder. To this solution was added 5 .0 grams of Triton Xl00 and 312 grams of zirconyl acetate solution. This formulation has 10.9% solids content and was used to treat the same kind of material as in Example 1 and in a similar manner. Physical property comparisons higher than that leaving the first padder. This procedure 65 are shown in Tables I and II.

TABLE I.WEATHER RESISTANCE OF FABRIC TREATED WITH TRIMETHYLOLMELAMINE Formula- I Breaking strength in Algae Sample Percent tion, N itrogen pounds gr0wth,*

add-on percent content 12 mos. solids 0 mos. 12 mos.

Example 1 14. 6 20 5.29 42 39 Example 2 U. 10.2 14. 9 3. 54 40 37 0 Example 3 8. 7 10. 9 2. 62 43 29 1+ Untreated control 47 17 Numerical value indicates amount of algae growth.

TABLE II.ROT RESISTANCE OF FABRIC TREATED WITH TRIMETHYLOLMELAMINE Formula- Strength retained after exposure Sample Percent tion, Nitrogen breaking strength in pounds add-on percent content solids week 1 week 6 weeks 14. 6 20 5. 29 42 45 47 10.2 14.9 3. 54 4O 42 46 pl 8. 7 10. 9 2.62 43 44 28 Untreated control 47 0 0 EXAMPLE 4- EXAMPLE 7 i led water at room tem erature To 1598 2 grams of d Sm p 10 To 348 grams of distilled water at room temperature was added with continuous stirring 412.8 grams of trimethylolmelamine powder. To this solution was added 5.0 grams of Triton X-lOO and a slurry containing 72.0 grams of titanium dioide (rutile) and 312 grams of zirconyl acetate solution. The TiO was used as an additional sunlight screener and as such helped to prevent actinic degradation of the cellulosic textile. This formulation has a 23.0%

is added with continuous stirring 86 grams of trimethyloleamine powder. To this solution was added 1.0 grams of Triton X100 and 65 grams of zirconyl acetate solution.

This solution was used to treat cotton printcloth in the usual padding procedure, and immediately afterward dried TABLE III.WEATHER RESISTANCE OF FABRIC TREATED WITH TRIMETHYLOLMELAMINE PLUS TITANIUM DIOXIDE Numerical value indicates amount of algae growth.

TABLE IV.ROT RESISTANCE OF FABRIC TREATED WITH TRIMETHYLOLMELAMINE PLUS TITANIUM DIOXIDE Formula- Strength retained after exposure- Sample Percent tion. Nitrogen breaking strength in pounds add-on percent content solids 0 week 1 week 6 weeks Example 4 18.9 23. 1 5. 29 44 47 49 Example 5 13.6 17.9 3. 55 43 45 46 Example 6 I. 11. 3 13.9 2. 51 43 46 28 Untreated control 47 0 0 solids content and was used to treat the same kind of material as in Example 1 and in a similar manner. Physical property comparisons are shown in Tables III and IV.

EXAMPLE 5 To 1720 grams of distilled water at room temperature in an oven at 85 C. for 5 minutes. It was then rolled onto a textile shell and left unwrapped at room temperature for days. The cure was effected by the time lapse.

This method of curing is our invention, and we refer to it as a delayed cure process. Tensile strength properties are shown in Table V.

TABLE V.-ROT RESISTANIEEIDOF FABRIC TREATED WITH TRIMETHYLOLMELAMINE GIVEN DELAYED CURE" Formula- Strength retained after exposure Sample Percent tion, Nitrogen breaking strength in pounds add-on percent content,

solids percent 0 week 1 week 6 weeks Example 7 15. 3 20 5. 2 45 47 52 Untreated c0ntr0l 44 0 0 was added with continuous stirring 288 grams of tri- EXAMPLE 8 methylolmelamine powder. To this solution was added 5.0 grams of Triton X-100 and a slurry consisting of 72.0 grams of TiO (rutile) and 312 grams of zirconyl acetate solution. This formulation has a 17.9% solids content and was used to treat the same kind of material as in Example 1 and in a similar manner. Physical property comparisons are shown in Tables III and 1V.

EXAMPLE 6 To 1819 grams of distilled water at room temperature was added with continuous stirring 192 grams of trimethylolmelarnine powder. To this solution was added 5.0 grams of Triton X-100 and a slurry consisting of 72.0 grams of TiO (rutile) and 312 grams of zirconyl acetate solution. This formulation has a 13.9% solids content and was used to treat the same kind of material as in Example 1 and in a similar manner. Physical property comparisons are shown in Tables III and IV.

EXAMPLE 9 To 60.5 grams of distilled water at room temperature was added with continuous stirring 26.5 grams of a methylated rnethylolmelamine, specifically Resin 841 solids content). To this solution was added 3 drops of Triton X100 and 13 grams of zirconyl acetate solution. This formulation of 20% solids content was used to treat the same kind of material as in Example 1 and in a similar 9 manner. Physical property comparisons are shown in Table VI.

EXAMPLE 10 ing of trimethylolmelamine and methylated methylolmelamine, about 13% of zirconyl acetate catalyst (22% ZrO and about 0.2% of a wetting agent,

(b) removing excess solution to obtain a wet pickup of about from 70% to 90%,

(c) drying the wet cellulosic textile at about from 75 to 95 C. for about from 3 to 5 minutes of time, the lower temperatures used with the longer periods of time, and

(d) curing the dry cellulosic textile at about from 120 to 160 C. for about from 4 to 8 minutes of time, the lower temperatures used with the longer periods of time.

METHYLO LMELAMINES For mula- Strength retained after exposure Sample Percent tion, Nitrogen breaking strength in pounds add-on percent content solids 0 week 1 week 6 weeks Aerotex M-3, Example 8. 14. 7 3. 8 42 46 39' Resin 841, Example 9 15. 0 20 3.6 42 37 Aerotex 23, Example 10.. 11.3 20 2. 1 40 38 25 Untreated control 0 0 EXAMPLE 11 To 1242 grams of distilled water at room temperature was added 258 grams of trimethylolmelamine and 1 gram of a wetting agent (Triton X-100) with continuous stirring. This solution was labeled Solution I, and set aside.

To 240 grams of distilled water at room temperature was added 260 grams of zirconyl acetate solution of 58.5% zirconyl acetate content. This solution was stirred well, labeled Solution II, and set aside.

An 8 inch by 20 foot length of 80 x 80 cotton printcloth was weighed and padded twice with Solution I to obtain a wet pickup of 83%. Immediately afterward the wet fabric was then padded once with Solution II. The fabric now wet with both solutions had a wet pickup of 92%. The wet pickup figures were both based on the weight of the untreated fabric.

The fabric was dried, after the second padding, in an oven for 4 minutes at 80 C., cured immediately thereafter for 4 minutes at 140 C., and process-washed. Finally the fabric was oven dried 4 minutes at 80 C.

The finished fabric was equilibrated and submitted to the usual testing. The treated fabric retained 84% of its original breaking strength, which is good. The nitrogen content was 3.8%

A portion of the treated fabric was placed in a rot bed together with untreated controls, and another portion likewise was submitted to weathering together with untreated controls. The portion submitted to the rot bed was submitted to breaking strength tests after being buried 6 weeks, and was found to have retained 100% of its original strength. The control was destroyed in the bed within one week. The portion submitted to weathering was removed for evaluation after having been on the weathering racks 9 months. The breaking strength tests indicated that the treated portion which was weathered had retained 99% of its original breaking strength, while the untreated control had retained merely 30% of its original breaking strength.

Upon close scrutiny of the weathered samples it was observed that the untreated control fabric had acquired a quantity of algae growth, while no such algae growth was evident on either surface of the treated and weathered fabric.

We claim:

1. A process for imparting to cellulosic textiles resistance to rot and weathering comprising (a) wetting the cellulosic textile with an aqueous solution containing about from 8 to 17.2% by weight of an aminoplast resin selected from the group consist- 2. The process of claim 1 wherein the aminoplast resin is trimethylolmelamine.

3. The process of claim 1 wherein the aminoplast resin is methylated methylolmelamine.

4. A process for imparting to cellulosic textiles resistance to rot, weathering, and actinic degradation comprising (a) wetting the cellulosic textile with an aqueous mixture containing about from 8 to 17.2% by weight of an aminoplast resin selected from the group consisting of trimethylolmelamine and methylated methylolmelamine, about 13% of zirconyl acetate catalyst (22% ZrO about 0.2% of a wetting agent, and about 3% of titanium dioxide,

(b) removing excess solution to obtain a wet pickup of about from 70% to (c) drying the Wet cellulosic textile at about from 75 to C. for about from 3 to 5 minutes of time, using the lower temperatures with the longer periods of time, and

(d) curing the dry cellulosic textile at about from to C. for about from 4 to 8 minutes of time, using the lower temperatures with the longer periods of time.

5. The process of claim 4 wherein the aminoplast resin is trimethylolmelamine.

6. The process of claim 4 wherein the aminoplast resin is methylated methylolmelamine.

7. A process for imparting to cellulosic textiles resistance to rot and weathering comprising (a) wetting the cellulosic textile with an aqueous solution containing about 17.2% by weight of an aminoplast resin selected from the group consisting of trimethylolmelamine and methylated methylolmelamine, and about 0.2% of a wetting agent,

(b) removing excess solution to obtain a wet pickup of about from 60% to 80%,

(c) further wetting the wet cellulosic textile from (b) with an aqueous solution containing about 30% of zirconyl acetate catalyst,

(d) removing excess of mixture of solutions to obtain a wet pickup of about from 10% to 30% higher than the wet pickup obtained in step (b),

(e) drying the wet cellulosic textile at about from 75 to 95 C. for about from 3 to 5 minutes of time, using the lower temperature with the longer periods of time, and

(f) curing the dry cellulosic textile at about from 120 1 1 1 2 to 160 C. for about from 4 to 8 minutes of time, 3,183,118 5/1965 Conner 117-138.5 using the lower temperatures with the longer periods 3,183,149 5/1965 Gonzales et a1. 117143 X of time. 3,317,345 5/1967 Pluck et a1. 117138.5 8. The process of claim 7 wherein the aminoplast resin 2,763,574 9/1956 Ruperti 117138.5 is trimethylolmelamine. 5

9. The process of claim 7 wherein the aminoplast resin WHJLLIAM MARTIN, Primary Examiner- IS methylated methylolmelamme- THEODORE o. DAVIS, Assistant Examiner.

References Cited s CL UNITED STATES PATENTS 2,938,815 5/1960 Van Bochove et a1. 117-143X 3,119,715 1/1964 Reeves et al. 117-1385 

1. PROCESS FOR IMPARTING TO CELLULOSIC TEXTILES RESISTANCE TO ROT AND WEATHERING COMPRISING (A) WETTING THE CELLULOSIC TEXTILE WITH AN AQUEOUS SOLUTION CONTAINING ABOUT FROM 8 TO 17.2% BY WEIGHT OF AN AMINOPLAST RESIN SELECTED FROM THE GROUP CONSISTING OF TRIMETHYLOLMELAMINE AND METHYLATED METHYLOL MELAMINE, ABOUT 13% OF ZIRCONYL ACETATE CATALYST (22% ZRO2), AND ABOUT 0.2% OF A WETTING AGENT, (B) REMOVING EXCESS SOLUTION TO OBTAIN A WET PICKUP OF ABOUT FROM 70% TO 90%, (C) DRYING THE WET CELLULOSIC TEXTILE AT ABOUT FROM 75* TO 95*C. FOR ABOUT FROM 3 TO 5 MINUTES OF TIME, THE LOWER TEMPERATURES USED WITH THE LONGER PERIODS OF TIME, AND (D) CURING THE DRY CELLUOSIC TEXTILE AT ABOUT FROM 120* TO 160*C. FOR ABOUT FROM 4 TO 8 MINUTES OF TIME, THE LOWER TEMPERATURES USED WITH THE LONGER PERIODS OF TIME. 